In situ gelling stimuli-sensitive block copolymer hydrogels for drug delivery

Journal of Controlled Release

Volumn 127, Issue 3, 2008, Pages 189-207

  He, Chaoliang ^a   Kim, Sung Wan ^b,c   Lee, Doo Sung ^a  

^a Sungkyunkwan University   (South Korea)

^b UNIVERSITY OF UTAH   (United States)

^c Hanyang University   (South Korea)

Author keywords

Block copolymer; Drug delivery; Hydrogel; Response; Stimuli sensitive

Indexed keywords

BLOCK COPOLYMER HYDROGELS; REVERSIBLE POLYMER NETWORKS; STIMULI SENSITIVE;

BLOCK COPOLYMERS; INTERPENETRATING POLYMER NETWORKS; MEDICAL APPLICATIONS; ORGANIC SOLVENTS; PH EFFECTS; PHASE TRANSITIONS; TOXICITY;

HYDROGELS;

ACRYLAMIDE DERIVATIVE; CEFTAZIDIME; COPOLYMER; CYCLOSPORIN A; DEXAMETHASONE; DEXTRAN; DIPYRIDAMOLE; FIBROBLAST GROWTH FACTOR; FLUORESCEIN ISOTHIOCYANATE; GLUCAGON LIKE PEPTIDE 1; GRANULOCYTE COLONY STIMULATING FACTOR; GROWTH HORMONE; HEPATITIS B SURFACE ANTIGEN; IMMUNOGLOBULIN G; INSULIN; INTERLEUKIN 2; KETOPROFEN; LEVONORGESTREL; LUCIFERASE; MACROGOL; PACLITAXEL; PHENOXYACETIC ACID; PLASMID DNA; POLOXAMER; POLYGLACTIN; POLYLACTIDE; REGEL; RG 13577; SPIRONOLACTONE; TESTOSTERONE; TRANSFORMING GROWTH FACTOR BETA1; UNCLASSIFIED DRUG;

AQUEOUS SOLUTION; CARBON NUCLEAR MAGNETIC RESONANCE; CHEMICAL STRUCTURE; DIFFERENTIAL SCANNING CALORIMETRY; DRUG DEGRADATION; DRUG DELIVERY SYSTEM; DRUG DISTRIBUTION; DRUG EFFICACY; DRUG FORMULATION; DRUG MECHANISM; DRUG METABOLISM; DRUG RELEASE; ENANTIOMER; GELATION; GENE DELIVERY SYSTEM; HEAT SENSITIVITY; HYDROGEL; HYDROPHILICITY; HYDROPHOBICITY; NON INSULIN DEPENDENT DIABETES MELLITUS; NONHUMAN; PH; PRIORITY JOURNAL; REVIEW; STIMULATION; TEMPERATURE; X RAY CRYSTALLOGRAPHY;

DRUG DELIVERY SYSTEMS; HYDROGELS; HYDROGEN-ION CONCENTRATION; POLYMERS; TEMPERATURE;

EID: 42049097246     PISSN: 01683659     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.jconrel.2008.01.005     Document Type: Review

References (173)

1. Qiu Y., and Park K. Environment-sensitive hydrogels for drug delivery. Advanced Drug Delivery Reviews 53 (2001) 321-329
2. Gupta P., Vermani K., and Grag S. Hydrogels: from controlled release to pH-responsive drug delivery. Drug Discovery Today 7 (2002) 569-579
3. Hoffman A.S. Hydrogels for biomedical applications. Advanced Drug Delivery Reviews 43 (2002) 3-12
4. Gil E.S., and Hudson S.M. Stimuli-responsive polymers and their bioconjugates. Progress in Polymer Science 29 (2004) 1173-1222
5. Bromberg L.E., and Ron E.S. Temperature-responsive gels and thermogelling polymer matrices for protein and peptide delivery. Advanced Drug Delivery Reviews 31 (1998) 197-221
6. Jeong B., Kim S.W., and Bae Y.H. Thermosensitive sol-gel reversible hydrogels. Advanced Drug Delivery Reviews 54 (2002) 37-51
7. Schmaljohann D. Thermo- and pH-responsive polymers in drug delivery. Advanced Drug Delivery Reviews 58 (2006) 1655-1670
8. Miyata T., Uragami T., and Nakamae K. Biomolecule-sensitive hydrogels. Advanced Drug Delivery Reviews 54 (2002) 79-98
9. Hatefi A., and Amsden B. Biodegradable injectable in situ forming drug delivery systems. Journal of Controlled Release 80 (2002) 9-28
10. Ruel-Gariepy E., and Leroux J.C. In situ-forming hydrogels-review of temperature-sensitive systems. European Journal of Pharmaceutics and Biopharmaceutics 58 (2004) 409-426
11. Schild H.G. Poly(N-isopropylacrylamide): experiment, theory and application. Progress in Polymer Science 17 (1992) 163-249
12. Taylor L.D., and Cerankowski L.D. Preparation of films exhibiting a balanced temperature dependence to permeation by aqueous solution-a study of low consolute behavior. Journal of Polymer Science: Polymer Chemistry Edition 13 (1975) 2551-2570
13. Horne R.A., Almeida J.P., Day A.F., and Yu N.T. Macromolecule hydration and the effect of solutions of polyvinyl methyl ether: a possible model for protein denaturation and temperature control in homeothermic animals. Journal of Colloid and Interface Science 35 (1971) 77-84
14. Aoshima S., Oda H., and Kobayashi E. Synthesis of thermally-induced phase separating polymer with well-defined polymer structure by living cationic polymerization. 1. Synthesis of poly(vinyl ether)s with oxyethylene units in the pendant and its phase separation behavior in aqueous solution. Journal of Polymer Science: Part A: Polymer Chemistry 30 (1992) 2407-2413
15. Suwa K., Wada Y., Kikunaga Y., Morishita K., Kishida A., and Akashi M. Synthesis and functionalities of poly(N-vinylalkylamide). IV. Synthesis and free radical polymerization of N-vinylisobutyramide) and thermosensitive of the polymers. Journal of Polymer Science: Part A: Polymer Chemistry 35 (1997) 1763-1768
16. Suwa K., Morishita K., Kishida A., and Akashi M. Synthesis and functionalities of poly(N-vinylalkylamide). V. Control of lower critical solution temperature of poly(N-vinylalkylamide). Journal of Polymer Science: Part A: Polymer Chemistry 35 (1997) 3087-3094
17. Mikheeva L.M., Grinberg N.V., Mashkevich A.Y., Grinberg V.Y., Thanh L.T.M., Makhaeva E.E., and Khokhlov A.R. Microcalorimetric study of thermal cooperation transitions in poly(N-vinylcaprolactam) hydrogels. Macromolecules 30 (1997) 2693-2699
18. Song S.C., Lee S.B., Jin J.I., and Sohn Y.S. A new class of biodegradable thermosensitive polymers. I. Synthesis and characterization of poly(organo phosphazenes) with methoxy-poly(ethylene glycol) and amino acid esters as side groups. Macromolecules 32 (1999) 2188-2193
19. Soga O., van Nostrum C.F., and Hennik W.E. Poly(N-(2-hydroxypropyl) methacrylamide mono/di lactate): a new class of biodegradable polymers with tunable thermosensitivity. Biomacromolecules 5 (2004) 818-821
20. Vermonden T., Besseling N.A.M., van Steenbergen M.J., and Hennik W.E. Rheological studies of thermosensitive triblock copolymer hydrogels. Langmuir 22 (2006) 10180-10184
21. Feil H., Bae Y.H., Feijen J., and Kim S.W. Effect of copolymer hydrophilicity and ionization on the lower critical solution temperature of N-isopropylacrylamide copolymers. Macromolecules 26 (1993) 2496-2500
22. Kohori F., Sakai K., Aoyagi T., Yokoyama M., Sakurai Y., and Okano T. Preparation and characterization of thermally responsive block copolymer micelles comprising poly(N-isopropylacrylamide-b-d,l-lactide). Journal of Controlled Release 55 (1998) 87-98
23. Lin H.H., and Cheng Y.L. In-situ thermoreversible gelation of block and star copolymers of poly(ethylene glycol) and poly(N-isopropylacrylamide) of varying architectures. Macromolecules 34 (2001) 3710-3715
24. Kwon I.K., and Matsuda T. Photo-inverter-based thermoresponsive block copolymers composed of poly(ethylene glycol) and poly(N-isopropylacrylamide) and chondrocyte immobilization. Biomaterials 27 (2006) 986-995
25. Li C., Tang Y., and Armes S.P. Synthesis and characterization of biocompatible thermo-responsive gelators based on ABA triblock copolymers. Biomacromolecules 6 (2005) 994-999
26. Li C., Buurma N.J., Haq I., Turner C., and Armes S.P. Synthesis and characterization of biocompatible, thermoresponsive ABC and ABA triblock copolymer gelators. Langmuir 21 (2005) 11026-11033
27. Tang T., Castelletto V., Parras P., Hamley I.W., King S.M., Roy D., Perrier S., Hoogenboom R., and Schubert U.S. Thermo-responsive poly(methyl methacrylate)-block-poly(N-isopropylacrylamide) block copolymers synthesized by RAFT polymerization: Micellization and gelation. Macromolecular Chemistry and Physics 207 (2006) 1718-1726
28. Aoshima S., and Sugihara S. Syntheses of stimuli-responsive block copolymers of vinyl ethers with side oxyethylene groups by living cationic polymerization and their thermosensitive physical gelation. Journal of Polymer Science: Part A: Polymer Chemistry 38 (2000) 3962-3965
29. Sugihara S., Kanaoka S., and Aoshima S. Double thermosensitive diblock copolymers of vinyl ethers with pendant oxyethylene groups: unique physical gelation. Macromolecules 38 (2005) 1919-1927
30. Aoshima S., and Hashimoto K. Stimuli-responsive block copolymers with polyalcohol segments: syntheses via living cationic polymerization of vinyl ethers with a silyoxyl group and their thermoreversible physical gelation. Journal of Polymer Science: Part A: Polymer Chemistry 39 (2001) 746-750
31. Sugihara S.J., Hashimoto K., Okabe S., Shibayama M., Kanaoka S., and Aoshima S. Stimuli-responsive diblock copolymers by living cationic polymerization: precision synthesis and highly sensitive physical gelation. Macromolecules 37 (2004) 336-343
32. Okabe S., Sugihara S., Aoshima S., and Shibayama M. Heat-induced self-assembling of thermosensitive block copolymer. 1. Small-angle neutron scattering study. Macromolecules 35 (2002) 8139-8146
33. Okabe S., Sugihara S., Aoshima S., and Shibayama M. Heat-induced self-assembling of thermosensitive block copolymer. Rheology and dynamic light scattering study. Macromolecules 36 (2003) 4099-4106
34. Sugihara S., Kanaoka S., and Aoshima S. Stimuli-responsive ABC triblock copolymers by sequential living cationic copolymerization: multistage self-assemblies through micellization to open association. Journal of Polymer Science: Part A: Polymer Chemstry 42 (2004) 2601-2611
35. Sugihara S., Hashimoto K., Matsumoto Y., Kanaoka S., and Aoshima S. Thermosensitive polyalcohols: synthesis via living cationic polymerization of vinyl ethers with a silyloxy groups. Journal of Polymer Science: Part A: Polymer Chemistry 41 (2003) 3300-3312
36. Yoshida T., Seno K., Kanaoka S., and Aoshima S. Stimuli-responsive reversible physical networks. 1. Synthesis and physical network properties of amphiphilic block and random copolymers with long alkyl chains by living cationic polymerization. Journal of Polymer Science: Part A: Polymer Chemistry 43 (2005) 1155-1165
37. Mortensen K., and Pedersen J.S. Structural study on the micelle formation of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer in aqueous solution. Macromolecules 26 (1993) 805-812
38. Alexandridis P., and Hatton T.A. Poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymer surfactants in aqueous solutions and at interfaces: thermodynamics, structure, dynamics, and modeling. Colloids and Surfaces A: Physicochemical and Engineering Aspects 96 (1995) 1-46
39. Dumortier G., Grossiord J.L., Agnely F., and Chaumeil J.C. A review of Poloxamer 407 pharmaceutical and pharmacological characteristics. Pharmaceutical Research 23 (2006) 2709-2728
40. Rassing J., and Attwood D. Ultrasonic velocity and light-scattering studies on the polyoxyethylene-polyoxypropylene copolymer F127 in aqueous solution. International Journal of Pharmaceutics 13 (1983) 47-55
41. Attwood D., Collett J.H., and Tait C.J. The micellar properties of the poly(oxyethylene)-poly(oxypropylene) copolymer Pluronic F127 in water and electrolyte solution. International Journal of Pharmaceutics 26 (1985) 25-33
42. Vadnere M., Amidon G., Lindenbaum S., and Haslam J.L. Thermodynamic studies on the gel-sol transition of some pluronic polyols. International Journal of Pharmaceutics 22 (1984) 207-218
43. Zhou Z., and Chu B. Light-scattering study on the association behavior of triblock polymers of ethylene oxide and propylene oxide in aqueous solution. Journal of Colloid and Interface Science 126 (1988) 171-180
44. Wanka G., Hoffmann H., and Ulbricht W. The aggregation behavior of poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene)-block-copolymers in aqueous solution. Colloid and Polymer Science 268 (1990) 101-117
45. Brown W., Schillen K., Almgren M., Hvidt S., and Bahadur P. Micelle and gel formation in a poly(ethylene oxide)/poly(propylene oxide)/poly(ethylene oxide) triblock block copolymer in water solution. Dynamic and static light scattering and oscillatory shear measurements. Journal of Physical Chemistry 95 (1991) 1850-1858
46. 27) in aqueous solution. Macromolecules 27 (1994) 6046-6054
47. Jorgensen E.B., Hvidt S., Brown W., and Schillen K. Effects of salts on the micellization and gelation of a triblock copolymer studied by rheology and light scattering. Macromolecules 30 (1997) 2355-2364
48. Song M.J., Lee D.S., Ahn J.H., Kim D.J., and Kimi S.C. Dielectric behavior during sol-gel transition of PEO-PPO-PEO triblock copolymer aqueous solution. Polymer Bulletin 43 (2000) 497-504
49. Mortensen K., and Brown W. Poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer in aqueous solution. The influence of relative block size. Macromolecules 26 (1993) 4128-4135
50. 40, in aqueous solution: micellisation, gelation and drug release. Journal of the Chemistry Society Faraday Transactions 89 (1993) 539-546
51. Yang Z., Pickard S., Deng N.J., Barlow R.J., Attwood D., and Booth C. Effect of block structure on the micellization and gelation of aqueous solutions of copolymers of ethylene oxide and butylenes oxide. Macromolecules 27 (1994) 2371-2379
52. Yu G.E., Yang Y.W., Yang Z., Attwood D., and Booth C. Association of diblock and triblock copolymers of ethylene oxide and butylenes oxide in aqueous solution. Langmuir 12 (1996) 3404-3412
53. Chaibundit C., Mai S.M., Heatlry F., and Booth C. Association properties of triblock copolymers in aqueous solution: copolymers of ethylene oxide and 1,2-butylene oxide with long E-blocks. Langmuir 16 (2000) 6945-9652
54. Cohn D., Sosnik A., and Levy A. Improved reverse thermo-responsive polymeric systems. Biomaterials 24 (2003) 3707-3714
55. Ahn J.S., Suh J.M., Lee M., and Jeong B. Slow eroding biodegradable multiblock poloxamer copolymers. Polymer International 54 (2005) 842-847
56. Sosnik A., and Cohn D. Reverse thermo-responsive poly(ethylene oxide) and poly(propylene oxide) multiblock copolymers. Biomaterials 26 (2005) 349-357
57. Xiong X.Y., Tam K.C., and Gan L.H. Synthesis and thermal responsive properties of P(LA-b-EO-b-PO-EO-b-LA) block copolymers with short hydrophobic poly(lactic acid) (PLA) segments. Polymer 46 (2005) 1841-1850
58. Xiong X.Y., Tam K.C., and Gan L.H. Synthesis and thermally responsive properties of novel pluronic F87/polycaprolactone (PCL) block copolymers with short PCL blocks. Journal of Applied Polymer Science 100 (2006) 4163-4172
59. Cohn D., Lando G., Sosnik A., Garty S., and Levi A. PEO-PPO-PEO-based poly(ether ester urethane)s as degradable reverse thermo-responsive multiblock copolymers. Biomaterials 27 (2006) 1718-1727
60. Jeong B., Bae Y.H., Lee D.S., and Kim S.W. Biodegradable block copolymers as injectable drug-delivery systems. Nature 388 (1997) 860-862
61. Jeong B., Lee D.S., Shon J., Bae Y.H., and Kim S.W. Thermoreversible gelation of poly(ethylene oxide) biodegradable polyester block copolymers. Journal of Polymer Science: Part A: Polymer Chemistry 37 (1999) 751-760
62. Choi S.W., Choi S.Y., Jeong B., Kim S.W., and Lee D.S. Thermoreversible gelation of poly(ethylene oxide) biodegradable polyester block copolymers. II. Journal of Polymer Science: Part A: Polymer Chemistry 37 (1999) 2207-2218
63. Li F., Li S., Ghzaoui A.E., Nouailhas H., and Zhuo R. Synthesis and gelation properties of PEG-PLA-PEG triblock copolymers obtained by coupling monohydroxylated PEG-PLA with adipoyl chloride. Langmuir 23 (2007) 2778-2783
64. Park S.Y., Han D.K., and Kim S.C. Synthesis and characterization of star-shaped PLLA-PEO block copolymers with temperature-sensitive sol-gel transition behavior. Macromolecules 34 (2001) 8821-8824
65. Park S.Y., Han B.R., Na K.M., Han D.K., and Kim S.C. Micellization and gelation of aqueous solutions of star-shaped PLLA-PEO block copolymers. Macromolecules 36 (2003) 4115-4124
66. Jeong B., Bae Y.H., and Kim S.W. Thermoreversible gelation of PEG-PLGA-PEG triblock copolymer aqueous solutions. Macromolecules 32 (1999) 7064-7069
67. Jeong B., Choi Y.K., Bae Y.H., Zentner G., and Kim S.W. New biodegradable polymers for injectable drug delivery systems. Journal of Controlled Release 62 (1999) 109-114
68. Jeong B., Bae Y.H., and King S.W. Biodegradable thermosensitive micelles of PEG-PLGA-PEG triblock copolymers. Colloids and Surfaces B: Biointerfaces 16 (1999) 185-193
69. Park M.J., and Char K. Gelation behavior of PEO-PLGA-PEO triblock copolymers induced by macroscopic phase separation. Langmuir 20 (2004) 2456-2465
70. Kwon K.W., Park M.J., Bae Y.H., Kim H.D., and Char K. Gelation behavior of PEO-PLGA-PEO triblock copolymers in water. Polymer 43 (2002) 3353-3358
71. Jeong B., Bae Y.H., and Kim S.W. In situ gelation of PEG-PLGA-PEG triblock copolymer aqueous solutions and degradation thereof. Journal of Biomedical Materials Research 50 (2000) 171-177
72. Jeong B., Bae Y.H., and Kim S.W. Drug release from biodegradable injectable thermosensitive hydrogel of PEG-PLGA-PEG triblock copolymers. Journal of Controlled Release 63 (2000) 155-163
73. Tyagi P., Li Z., Chancellor M., Groat W.C.D., Yoshimura N., and Huang L. Sustained intravesical drug delivery using thermosensitive hydrogel. Pharmaceutical Research 21 (2004) 832-837
74. Li Z., Ning W., Wang J., Choi A., Lee P.Y., Tyagi P., and Huang L. Controlled gene delivery system based on thermosensitive biodegradable hydrogel. Pharmaceutical Research 20 (2003) 884-888
75. Lee P.Y., Li Z., and Huang L. Thermosensitive hydrogel as a Tgf-b1 gene delivery vehicle enhances diabetic wound healing. Pharmaceutical Research 20 (2003) 1995-2000
76. Lee D.S., Shim M.S., Kim S.W., Lee H., Park I., and Chang T. Novel thermoreversible gelation of biodegradable PLGA-block-PEO-block-PLGA triblock copolymers in aqueous solution. Macromolecular Rapid Communications 22 (2001) 587-592
77. Zentner G.M., Rathi R., Shih C., Mcrea J.C., Seo M.H., Oh H., Rhee B.G., Mestecky J., Moldoveanu Z., Morgan M., and Weitman S. Biodegradable block copolymers for delivery of proteins and water-insoluble drugs. Journal of Controlled Release 72 (2001) 203-215
78. Shim M.S., Lee H.T., Shim W.S., Park I., Lee H., Chang T., Kim S.W., and Lee D.S. Poly(d,l-lactic acid-co-glycolic acid)-b-poly(ethylene glycol)-b-poly(d,l-lactic acid-co-glycolic acid) triblock copolymer and thermoreversible phase transition in water. Journal of Biomedical Materials Research 61 (2002) 188-196
79. Kim Y.J., Choi S., Koh J.J., Lee M., Ko K.S., and Kim S.W. Controlled release of insulin from injectable biodegradable triblock copolymer. Pharmaceutical Research 18 (2001) 548-550
80. Choi S., and Kim S.W. Controlled release of insulin from injectable biodegradable triblock copolymer depot in ZDF rats. Pharmaceutical Research 20 (2003) 2008-2010
81. Choi S., Baudys M., and Kim S.W. Control of blood glucose by novel GLP-1 delivery using biodegradable triblock copolymer of PLGA-PEG-PLGA in type-2 diabetic rats. Pharmaceutical Research 21 (2004) 827-831
82. Chen S., and Singh J. Controlled delivery of testosterone from smart polymer solution based systems: in vitro evaluation. International Journal of Pharmaceutics 295 (2005) 183-190
83. Chen S., and Singh J. In vitro release of levonorgestrel from phase sensitive and thermosensitive smart polymer delivery systems. Pharmaceutical Development and Technology 10 (2005) 319-325
84. Samlowski W.E., McGregor J.R., Jurek M., Baudys M., Zentner G.M., and Fowers K.D. ReGel® polymer-based delivery of interleukin-2 as a cancer treatment. Journal of Immunotheraphy 29 (2006) 524-535
85. Lin H., Tian H.Y., Sun J.R., Zhuang X.L., Chen X.S., Li Y.S., and Jing X.B. Synthesis, characterization and drug release of temperature-sensitive PLGA-PEG-PLGA hydrogel. Chemical Journal of Chinese Universities 27 (2006) 1385-1388
86. Zhong Z., Dijkstra P.J., Feijen J., Kwon Y.M., Bae Y.H., and Kim S.W. Synthesis and aqueous phase behavior of thermoresponsive biodegradable poly(d,l-3-methylglycolide)-block-poly(ethylene glycol)-block-poly(d,l-3-methyl-glycolide) triblock copolymers. Macromolecular Chemistry and Physics 203 (2002) 1797-1803
87. Qiao M., Chen D., Ma X., and Liu Y. Injectable biodegradable temperature-responsive PLGA-PEG-PLGA copolymers: synthesis and effect of copolymer composition on the drug release from the copolymer-based hydrogels. International Journal of Pharmaceutics 294 (2005) 103-112
88. Yu L., Zhang H., and Ding J. A subtle end-group effect on macroscopic physical gelation of triblock copolymer aqueous solutions. Angewandte Chemie International Edition 45 (2006) 2232-2235
89. Yu L., Chang G., Zhang H., and Ding J. Temperature-induced spontaneous sol-gel transition of poly(d,l-lactic acid-co-glycolic acid)-b-poly(ethylene glycol)-b-poly(d,l-lactic acid-co-glycolic acid) triblock copolymers and their end-capped derivatives in water. Journal of Polymer Science: Part A: Polymer Chemistry 45 (2007) 1122-1133
90. Jo S., Kim J., and Kim S.W. Reverse thermal gelation of aliphatically modified biodegradable triblock copolymers. Macromolecular Bioscience 6 (2006) 923-928
91. Lee S.J., Han B.R., Park S.Y., Han D.K., and Kim S.C. Sol-gel transition behavior of biodegradable three-arm and four-arm star-shaped PLGA-PEG block copolymer aqueous solution. Journal of Polymer Science: Part A: Polymer Chemistry 44 (2006) 888-899
92. Kim M.S., Seo K.S., Khang G., Cho S.H., and Lee H.B. Preparation of methoxy poly(ethylene glycol)/polyester diblock copolymers and examination of the gel-to-sol transition. Journal of Polymer Science: Part A: Polymer Chemistry 42 (2004) 5784-5793
93. Yang J., Jia L., Hao Q., Li Y., Li Q., Fang Q., and Cao A. A novel approach to biodegradable block copolymers of ε-caprolactone and δ-valerolactone catalyzed by new aluminum metal complexes II. Micellization and solution to gel transition. Macromolecular Bioscience 5 (2005) 896-903
94. Kim M.S., Seo K.S., Khang G., Cho S.H., and Lee H.B. Preparation of poly(ethylene glycol)-block-poly(caprolactone) copolymers and their applications as the thermo-sensitive materials. Journal of Biomedical Materials Research 70A (2004) 154-158
95. Kim M.S., Hyun H., Khang G., and Lee H.B. Preparation of thermosensitive diblock copolymers consisting of MPEG and polyesters. Macromolecules 39 (2006) 3099-3102
96. Kim M.S., Hyun H., Seo K.S., Cho Y.H., Lee J.W., Lee C.R., Khang G., and Lee H.B. Preparation and characterization of MPEG-PCL diblock copolymers with thermo-responsive sol-gel-sol phase transition. Journal of Polymer Science: Part A: Polymer Chemistry 44 (2006) 5413-5423
97. Kim M.S., Kim S.K., Kim S.H., Hyun H., Khang G., and Lee H.B. In vivo osteogenic differentiation of rat bone marrow stromal cells in thermosensitive MPEG-PCL diblock copolymer gels. Tissue Engineering 12 (2006) 2863-2873
98. Hyun H., Kim Y.H., Song I.B., Lee J.W., Kim M.S., Khang G., Park K., and Lee H.B. In vitro and in vivo release of albumin using a biodegradable MPEG-PCL diblock copolymer as an in situ gel-forming carrier. Biomacromolecules 8 (2007) 1093-1100
99. Song M.J., Lee D.S., Ahn J.H., Kim D.J., and Kim S.C. Thermosensitive sol-gel transition behavior of poly(ethylene oxide)/aliphatic polyester/poly(ethylene oxide) aqueous solutions. Journal of Polymer Science: Part A: Polymer Chemistry 42 (2004) 772-784
100. Behravesh E., Shung A.K., Jo S., and Mikos A.G. Synthesis and characterization of triblock copolymers of methoxy poly(ethylene glycol) and poly(propylene fumarate). Biomacromolecules 3 (2002) 153-158
101. Behravesh E., Jo S., Zygourakis K., and Mikos A.G. Synthesis of in situ cross-linkable macroporous biodegradable poly(propylene fumarate-co-ethylene glycol) hydrogels. Biomacromolecules 3 (2002) 374-381
102. Hwang M.J., Suh J.M., Bae Y.H., Kim S.W., and Jeong B. Caprolactonic poloxamer analog: PEG-PCL-PEG. Biomacromolecules 6 (2005) 885-890
103. Bae S.J., Suh J.M., Sohn Y.S., Bae Y.H., Kim S.W., and Jeong B. Thermogelling poly(carprolactone-b-ethylene glycol-b-caprolactone) aqueous solutions. Macromolecules 38 (2005) 5260-5265
104. Bae S.J., Joo M.K., Jeong Y., Kim S.W., Lee W., Sohn Y.S., and Jeong B. Gelation behavior of poly(ethylene glycol) and polycaprolactone triblock and multiblock copolymer aqueous solutions. Macromolecules 39 (2006) 4873-4879
105. Huh K.M., and Bae Y.H. Synthesis and characterization of poly(ethylene glycol)/poly(l-lactic acid) alternating multiblock copolymers. Polymer 40 (1999) 6147-6155
106. Bae Y.H., Huh K.M., Kim Y., and Park K.H. Biodegradable amphiphilic multiblock copolymers and their implications for biomedical applications. Journal of Controlled Release 64 (2000) 3-13
107. Lee J., Bae Y.H., Sohn Y.S., and Jeong B. Thermogelling aqueous solutions of alternating multiblock copolymers of poly(l-lactic acid) and poly(ethylene glycol). Biomacromolecules 7 (2006) 1729-1734
108. Joo M.K., Sohn Y.S., and Jeong B. Stereoisomeric effect on reverse thermal gelation of poly(ethylene glycol)/poly(lactide) multiblock copolymers. Macromolecules 40 (2007) 5111-5115
109. Lee J.W., Hua F.J., and Lee D.S. Thermoreversible gelation of biodegradable poly(ε-caprolactone) and poly(ethylene glycol) multiblock copolymers in aqueous solutions. Journal of Controlled Release 73 (2001) 315-327
110. Lee S.C., Kang S.W., Kim C., Kwon I.C., and Jeong S.Y. Synthesis and characterization of amphiphilic poly(2-ethyl-2-oxazoline)/poly(ε-caprolactone) alternating multiblock copolymers. Polymer 41 (2000) 7091-7097
111. Li F., Li S., and Vert M. Synthesis and rheological properties of polylactide/poly(ethylene glycol) multiblock copolymers. Macromolecular Bioscience 5 (2005) 1125-1131
112. Lee J., Joo M.K., Oh H., Sohn Y.S., and Jeong B. Injectable gel: poly(ethylene glycol)-sebacic acid polyester. Polymer 47 (2006) 3760-3766
113. Loh X.J., Goh S.H., and Li J. New biodegradable thermogelling copolymers having very low gelation concentrations. Biomacromolecules 8 (2007) 585-593
114. de Jong S.J., De Smedt S.C., Wahls M.W.C., Demeester J., Kettenes-van den Bosch J.J., and Hennink W.E. Novel self-assembled hydrogels by stereocomplex formation in aqueous solution of enantiomeric lactic acid oligomers grafted to dextran. Macromolecules 33 (2000) 3680-3686
115. Fujiwara T., Mukose T., Yamaoka T., Yamane H., Sakurai S., and Kimura Y. Novel thermo-responsive formation of a hydrogel by stereo-complexation between PLLA-PEG-PLLA and PDLA-PEG-PDLA block copolymers. Macromolecular Bioscience 1 (2001) 204-208
116. Mukose T., Fujiwara T., Nakano J., Taniguchi I., Miyamoto M., Kimura Y., Teraoka I., and Lee C.W. Hyfrogel formation between enantiomeric B-A-B-type block copolymers of polylactides (PLLA or PDLA:A) and polyoxyethylene (PEG:B); PEG-PLLA-PEG and PEG-PDLA-PEG. Macromolecular Bioscience 4 (2004) 361-367
117. Li S., and Vert M. Synthesis, characterization, and stereocomplex-induced gelation of block copolymers prepared by ring-opening polymerization of l(d)-lactide in the presence of poly(ethylene glycol). Macromolecules 36 (2003) 8008-8014
118. 8 block copolymers. Macromolecular Symposia 224 (2005) 119-131
119. 8 star block copolymers. Biomacromolecules 7 (2006) 2790-2795
120. Hiemstra C., Zhong Z., Van Tomme S.R., van Steenbergen M.J., Jacobs J.J.L., Otter W.D., Hennink W.E., and Feijen J. In vitro and in vivo protein delivery from in situ forming poly(ethylene glycol)-poly(lactide) hydrogels. Journal of Controlled Release 119 (2007) 320-327
121. Hiemstra C., Zhong Z.Y., Jiang X., Hennink W.E., Dijkstra P.J., and Feijen J. PEG-PLLA and PEG-PDLA multiblock copolymers: synthesis and in situ hydrogel formation by stereocomplexation. Journal of Controlled Release 116 (2006) e17-e19
122. Kim S.Y., Kim H.J., Lee K.E., Han S.S., Sohn Y.S., and Jeong B. Reverse thermal gelling PEG-PTMC diblock copolymer aqueous solution. Macromolecules 40 (2007) 5519-5525
123. Choi B.G., Sohn Y.S., and Jeong B. Closed-loop sol-gel transition of PEG-PEC aqueous solution. Journal of Physical Chemistry B 111 (2007) 7715-7718
124. Philippova O.E., Hourdet D., Audebert R., and Khokhlov A.R. pH-responsive gels of hydrophobically modified poly(acrylic acid). Macromolecules 30 (1997) 8278-8285
125. Torres-Lugo M., and Peppas N.A. Molecular design and in vitro studies of novel pH-sensitive hydrogels for the oral delivery of calcitonin. Macromolecules 32 (1999) 6646-6651
126. Yang Z., Zhang Y., Markland P., and Yang V.C. Poly(glutamic acid) poly(ethylene glycol) hydrogels prepared by photoinduced polymerization: synthesis, characterization, and preliminary release studies of protein drugs. Journal of Biomedical Materials Research 62 (2002) 14-21
127. Park S.Y., and Bae Y.H. Novel pH-sensitive polymers containing sulfonamide groups. Macromolecular Rapid Communications 20 (1999) 269-273
128. Butun V., Armes S.P., and Billingham N.C. Synthesis and aqueous solution properties of near-monodisperse tertiary amine methacrylate homopolymers and diblock copolymers. Polymer 42 (2001) 5993-6008
129. Gohy J., Lohmeijer B.G.G., Varshney S.K., Decamps B., Leroy E., Boileau S., and Schubert U.S. Stimuli-responsive aqueous micelles from an ABC metallo-supramolecullar triblock copolymer. Macromolecules 35 (2002) 9748-9755
130. Lynn D.M., Amiji M.M., and Langer R. pH-responsive polymer microsphere: rapid release of encapsulated material within the range of intracellular pH. Angewandte Chemie International Edition 40 (2001) 1707-1710
131. Ma Y., Tang Y., Billingham N.C., and Armes S.P. Synthesis of biocompatible, stimuli-responsive, physical gels based on ABA triblock copolymers. Biomacromolecules 4 (2003) 864-868
132. Castelletto V., Hamley I.W., Ma Y., Bories-Azeau X., Armes S.P., and Lewis A.L. Microstructure and physical properties of a pH-responsive gel based on a novel biocompatible ABA-type triblock copolymer. Langmuir 20 (2004) 4306-4309
133. Tsitsilianis C., Iliopoulos I., and Ducouret G. An associative polyelectrolyte end-capped with short polystyrene chains. Synthesis and rheological behavior. Macromolecules 33 (2000) 2936-2943
134. Tsitsilianis C., and Iliopoulos I. Viscoelastic properties of physical gels formed by associative telechelic polyelectrolytes in aqueous in aqueous media. Macromolecules 35 (2002) 3662-3667
135. Katsampas I., and Tsitsilianis C. Hierarchical self-organization of ABC terpolymer constituted of a long polyelectrolyte end-capped by different hydrophobic blocks. Macromolecules 38 (2005) 1307-1314
136. Gotzmanis G.T., Tsitsilianis C., Hadjiyannakou S.C., Patrickios C.S., Lupitskyy R., and Minko S. Cationic telechelic polyelectrolytes: Synthesis by groups transfer polymerization and self-organization in aqueous media. Macromolecules 39 (2006) 678-683
137. van de Wetering P., Zuidam N.J., van Steenbergen M.J., van der Houwen O.A.G.J., Underberg W.J.M., and Hennink W.E. A mechanistic study of the hydrolytic stability of poly(2-(dimethylamino)ethyl methacrylate). Macromolecules 31 (1998) 8063-8068
138. Bossard F., Aubry T., Gotzamanis G., and Tsitsilians C. pH-tunable rheological properties of a telechelic catonic polyelectrolyte reversible hydrogel. Soft Matter 2 (2006) 510-516
139. Sfika V., and Tsitsilians C. Association phenomena of poly(acrylic acid)-b-poly(2-vinylpyridine)-b-poly(acrylic acid) triblock polyampholyte in aqueous solutions: from transient network to compact micelles. Macromolecules 36 (2003) 4983-4988
140. Bossard F., Sfika V., and Tsitsilians C. Rheological properties of physical gel formed by triblock polyampholyte in salt-free aqueous solutions. Macromolecules 37 (2004) 3899-3904
141. Katsampas I., Roiter Y., Minko S., and Tsitsilians C. Multifunctional stimuli responsive ABC terpolymers: from three-compartment micelles to three-dimensional network. Macromolecular Rapid Communications 26 (2005) 1371-1376
142. Anderson B.C., Cox S.M., Bloom P.D., Sheares V.V., and Mallapragada S.K. Synthesis and characterization of diblock and gel-forming pentablock copolymers of tertiary amine methacrylates, poly(ethylene glycol), and poly(propylene glycol). Macromolecules 36 (2003) 1670-1676
143. Determan M.D., Cox J.P., Seifert S., Thiyagarajan P., and Mallapragada S.K. Synthesis and characterization of temperature and pH-responsive pentablock copolymers. Polymer 46 (2005) 6933-6946
144. Determan M.D., Cox J.P., and Mallapragada S.K. Drug release from pH-responsive thermogelling pentablock copolymers. Journal of Biomedical Materials Research 81A (2007) 326-333
145. Suh J.M., Bae S.J., and Jeong B. Thermogelling multiblock poloxamer aqueous solutions with closed-loop sol-gel-sol transitions upon increasing pH. Advanced Materials 17 (2005) 118-120
146. Park S.Y., Lee Y., Bae K.H., Ahn C.H., and Park T.G. Temperature/pH-sensitive hydrogels prepared from Pluronic copolymers end-capped with carboxylic acid groups via an oligolactide spacer. Macromolecular Rapid Communications 28 (2007) 1172-1176
147. Shim W.S., Kim J.H., Park H., Kim K., Kwon I.C., and Lee D.S. Biodegradability and biocompatibility of a pH- and thermo-sensitive hydrogel formed from a sulfonamide-modified poly(ε-caprolactone-co-lactide)-poly(ethylene glycol)-poly(ε-caprolactone-co-lactide) block copolymer. Biomaterials 27 (2006) 5178-5185
148. Shim W.S., Yoo J.S., Bae Y.H., and Lee D.S. Novel injectable pH and temperature sensitive block copolymer hydrogels. Biomacromolecules 6 (2005) 2930-2934
149. Shim W.S., Kim S.W., and Lee D.S. Sulfonamide-based pH- and temperature-sensitive biodegradable block copolymer hydrogels. Biomacromolecules 7 (2006) 1935-1941
150. Shim W.S., Kim J.H., Kim K., Kim Y.S., Park R.W., Kim I.S., Kwon I.C., and Lee D.S. pH- and temperature-sensitive, injectable, biodegradable block copolymer hydrogels as carries for paclitaxel. International Journal of Pharmaceutics 331 (2007) 11-18
151. Dayananda K., Pi B.S., Kim B.S., Park T.G., and Lee D.S. Synthesis and characterization of pH/temperature-sensitive block copolymers via atom transfer radical polymerization. Polymer 48 (2007) 758-762
152. Huynh D.P., Shim W.S., Kim J.H., and Lee D.S. pH/temperature sensitive poly(ethylene glycol)-based biodegradable polyester block copolymer hydrogels. Polymer 47 (2006) 7918-7926
153. Lynn D.M., and Langer R. Degradable poly(β-amino ester): synthesis, characterization, and self-assembly with plasmid DNA. Journal of the American Chemical Society 122 (2000) 10761-10768
154. Yoo J.S., Kim M.S., Lee D.S., Kim B.S., and Kim J.H. Novel pH and temperature-sensitive block copolymer: poly(ethylene glycol)-b-poly(ε-caprolactone)-b-poly(β-amino ester). Macromolecular Research 14 (2006) 117-120
155. D.P. Huynh, M.K. Nguyen, B.S. Pi, M.S. Kim, S.Y. Chae, K.C. Lee, B.S. Kim, S.W. Kim, D.S. Lee, A new functionalized injectable hydrogel for controlled insulin delivery, Biomaterials in press.
156. Wintersteiner O., and Abramson H.A. The isoelectric point of insulin: electrical properties of adsorbed and crystalline insulin. Journal of Biological Chemistry 99 (1933) 741-753
157. Angelopoulos S.A., and Tsitsilianis C. Thermo-responsive hydrogels based on poly(N,N-diethylacrylamide)-block-poly(acrylic acid)-block-poly(N,N-diethyl-acryl amide) double hydrophilic triblock copolymer. Macromolecular Chemistry and Physics 207 (2006) 2188-2194
158. Li Y., Tang Y., Narain R., Lewis A.L., and Armes S.P. Biomimetic stimulus-responsive star diblock gelators. Langmuir 21 (2005) 9946-9954
159. Yao L., and Krause S. Electromechanical responses of strong acid polymer gels in DC electric fields. Macromolecules 36 (2003) 2055-2065
160. Filipcsei G., Feher J., and Zrinyi M. Electric field sensitive neutral polymer gels. Journal of Molecular Science 554 (2000) 109-117
161. Murdan S. Electro-responsive drug delivery from hydrogels. Journal of Controlled Release 92 (2003) 1-17
162. Xulu P.M., Filipcsei G., and Zrinyi M. Preparation and responsive properties of magnetically soft poly(N-isopropylacrylamide) gels. Macromolecules 33 (2000) 1716-1719
163. Liu T.Y., Hu S.H., Liu K.H., Liu D.M., and Chen S.Y. Preparation and characterization of smart magnetic hydrogels and its use for drug release. Journal of Magnetism and Magnetic Materials 304 (2006) e397-e399
164. Mamada A., Tanaka T., Kungwatchakun D., and Irie M. Photoinduced phase transition of gels. Macromolecules 23 (1990) 1517-1519
165. Suzuki A., and Tanaka T. Phase transition in polymer gels induced by visible light. Nature 346 (1990) 345-347
166. Liu H.Q., Zhen M., and Wu R.H. Ionic-strength- and pH-responsive poly[acrylamide-co-(maleic acid)] hydrogel nanofibers. Macromolecular Chemistry and Physics 208 (2007) 874-880
167. Traitel T., Cohen Y., and Kost J. Characterization of glucose-sensitive insulin release systems in simulated in vivo conditions. Biomaterials 21 (2000) 1679-1687
168. Kang S.I., and Bae Y.H. A sulfonamide based glucose-responsive hydrogel with covalently immobilized glucose oxidase and catalase. Journal of Controlled Release 86 (2003) 115-121
169. Hovgaard L., and Brondsted H. Dextran hydrogels for colon-specific drug delivery. Journal of Controlled Release 36 (1995) 159-166
170. Miyata T., Asami N., and Uragami T. A reversibly antigen-responsive hydrogel. Nature (1999) 766-769
171. Sun K.H., Sohn Y.S., and Jeong B. Thermogelling poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) disulfide multiblock copolymer as a thiol-sensitive degradable polymer. Biomacromolecules 7 (2006) 2871-2877
172. Russo A., DeGraff W., Friedman N., and Mitchell J.B. Selective modulation of glutathione levels in human normal versus tumor cells and subsequent differential response to chemotherapy drugs. Cancer Research 46 (1986) 2845-2848
173. Lee Y., Koo H., Jin G., Mo H., Cho M.Y., Park J.Y., Choi J.S., and Park J.S. Poly(ethylene oxide sulfide): new poly(ethylene glycol) derivatives degradable in reductive conditions. Biomacromolecules 6 (2005) 24-26